Mercerizing lyes and a process for their manufacture



' lye and impart thereto a powerful wetting-out- Patented May 9, 1939IVIERCERIZING LYES AND A PROCESS FOR THEIR MANUFACTURE Heinrich Lier,Basel, Switzerland, assignor to the firm of Chemical Works FormerlySandoz,

Basel, Switzerland No Drawing. Application January 7, 1937, Se-

rial No. 119,528. 1936 In Switzerland January 9,

8 Claims. (01. 8-427) The present invention relates to a process forimproving the wetting-out properties of alkaline lyes of at least 18 B.and to such improved lyes and is based on the use of naphthenic acids assuch or in combination with emulsifying agents of non-phenolic characteror with aminoor ether alcohols.

Until now it has only been known that naphthenic acids which are aby-product in the manufacture of petrol can be used in dilute alkalinesolutions the specific gravity of which is not higher than 1 B. It hasalways been thought that these acids cannot be used in concentrated lyesbecause of their poor solubility.

The present invention resides on the observation that naphthenic acidscan very well be used alone as wetting agents in concentrated alkalinelyes say from 18 B. upwards, if their molecular weight or their acidnumber is adapted to the concentration of the lye.

According to the present invention concentrated alkaline lyes possessingexcellent Wettingout power are prepared by adding thereto smallquantities of selected fractions of naphthenic acids, whereby theselection is so made that th quotient acid number of the naphthenic acidfraction content in percent of alkali in the lye must be a numberbetween and 25. This mathematical expression means that for lyes oflower concentration fractions of naphthenic acids with a low acid numberare used, whereas for concentrated lyes naphthenic acids possessing ahigh acid number will be employed. Instead of the expression acid numberit is also possible to say molecular weight, as a low acid number of afraction indicates high molecular naphthenic acids, and a high acidnumber indicates low molecular acids. It the acid number is adapted tothe concentration of the lye by following the above mathematical rule,the naphthenic acid fraction will generally be clearly soluble in theand penetrating action for raw cellulosic fibres. Such a lye will thenbe of great advantage for the treatment of cellulosic material, forinstance for the mercerisation of raw unbowked cotton or thealkalisation of raw paper pulp in the manufacture of rayon.

The acid number of naphthenic acids varies between 250 and 500 and ifthe above rule is followed, it will be clear that for sodium hydroxidelyes of 30 B. and upwards, naphthenic acid fractions possessing the acidnumber 380 and upr ups.

wards will be preferably used. For caustic soda lyes of about 26-30 B.fractions with the acid number of about 360-380 are preferable. For moredilute lyes say of 22-26 B. fractions with the acid number of about320-360 are suitable. If dilute lyes, say of 18-22" B., are used, thenthe corresponding acid number of the naphthenic acidfractions will be of250-320.

It has further been observed that the wettingout power of naphthenicacids can be increased if the above quotient increases in value byadding t ereto a small amount of aminoor ether alcoho s. In the case thequotient sinks, then the activity of the naphthenic acids can beincreased by adding theretma certain amount of emulsifying agents of anonphenolic character.

This means that when naphthenic acid fractions of low molecular weightare used in rather dilute alkaline lyes, they obtain the property ofemulsifying therein substances like aminoor ether alcohols, which thenincrease the wettingout power of alkaline lyes. For instance ifnaphthenic acid fractions with the acid number 380 and upwards are usedin lyes of say 22-28 B., it is indicated to add to the naphthenic acidsa small amount of aminoor ether alcohols and to use such mixtures aswetting agent, which will then increase the wetting-out properties ofalkaline lyes much stronger than if the naphthenic acids fractions areused alone.-

In case that naphthenic acids of high molecular weight or of low acidnumber are used in concentrated alkaline lyes, it happens that they areno more completely soluble therein and instead of clear solutions, muddyalkaline lyes are obtained. In such a case it has been observed that. itis possible to increase the wetting-out power of naphthenic acid and toprepare clear soluble mixr tures by adding to the naphthenic acidfraction a certain amount of emulsifying agents of generally acidcharacter or belonging to the glucoside type containing at least fouraliphatic hydroxy For instance if a naphthenic acid fraction with theacid number 384 is used alone in lyes of 30-34" B., a muddy lye isobtained because the naphthenic acids are no more clearly soluble insuch lyes. But if to such naphthenic acids a certain amount of anemulsifying agent like butylsulphate is added; then the mixtures therebyobtained become clearly soluble in lyes of such concentration and impartthereto a verypowerful wetting-out action.

As ether alcohols saturated and unsaturated compounds of thealiphatic,cycloaliphatic, aralian ether linkage at least one aliphatic hydroxygroup, such as the ethers of glycol, glycerine and polyvalent alcohols,the acetalsv derived from polyvalent alcohols and ketones or aldehydescan 5 be used. As amino alcohols compounds containing one. or morenitrogen atoms and one or more oxalkyl groups in the molecule aresuitable for improving the wetting-out properties of the fractions ofnaphthenic acids. In case that the" use of an emulsifying agent isindicated, derivatives are used which belong to the class of sulphonicacids of alkylated aromatic compounds, aliphatic and heterocyclicsulphonic acids with at least three carbon atoms in the molecule, thesulphuric esters of aliphatic alcohols with 2 to 12 carbon atomspossessing straight or ramified carbon chains, the sulphuric acid estersof etherand amino alcohols, aliphatic saturated or unsaturatedmonocarboxylic acids with 3 to 12 carbon atoms and with straightramified carbon chains, which chains can eventually contain oxygenbridges; such cids are for example isobutyric acid, isovaleri nic acid,isocapronic acid, isobutylacetic acid, isoamyl acetic acid,methylisobutyl acetic acid, methylisoamyl acetic acid, ethylpropylacetic acid, dipropyl acetic acid, 1:3- dimethyl valerianic acid,3-n1ethyl capronic acid, lziii-dimethyl capronic acid, S-methyl-caprylacid 30 naphthenic acid fractions with aminoor ether alcohols in thecase that the quotient acid number of the naphthenic acid fractioncontent in percent of alkali in the lye acid number of the naphthenicacid fraction content in percent of alkali in the lye is a number lowerthan 15.

Still another object of the present invention are the alkaline lyes of18 B. and more containing suitable fractions of naph'thenic acidinmixture with aminoor ether alcohols or in mixture with emulsifyingagents of an'acid character and the process of treating cellulosicmaterial, especially the mercerizing process of cellulosic fibres withthe said lyes.

The following first table and examples show how the present inventioncan practically be carried out, the parts-being by weight, or whereespecially indicated by volume:

Table I Degrees Cc. Percent Percent Percent 25. 5 32 10 4. 6 l1. l6. 415. 45 24. 5 31 10 8. 0 16. 4 20. 8 16. 1 23. 5 30 10 9.2 17. 0 20. 816. 76 21. 5 28 10 9. 3 16. 5 l9. 4 l8. 3 18. 7 25 10 v 9. 3 14. 7 16. 721. 07 23. 5 30 7. 5 6. 3 l4. 2 l9. 2 16. 34 40 23.5 30 5 r 21.0 16.55

384 g g: g (7) 19. 2 21. 6 17. 0

. 19. 130 140 Roumanian 011- 358 19 5 5 21 6 86 gm 26 5 .13. 4 19.6 21.(i 130-140 American origin. 384 18. 7 25 5 9. 2 15. 2 17. 0 130-440American origin- 384 18. 7 25 7. 5 11. 4 17. 0 l8. 6 20. 53 140-150 35618. 7 25 3 10. 0 l5. 4 17. 7 4 5 18.7 25 5 14. 9 20. 3 22. 0 19. 0

etc. (see British Patent No. 414,485), the glycosido-compoundsobtainable fromsugars and aliphatic. alcohols or ether alcohols.

One object of the present invention is therefore a process for improvingthe wetting-out power of. alkaline lyes of a concentration superior to18 B. by adding thereto fractions of naphthenic acid selected in such amanner that the quotient acid number of the naphflienic acid fractioncontent in percent of alkali in the lye is a number between and 25.

Another object of the. present invention is. a process for improving thewetting-out action of alkaline lyes by adding to concentrated lyesnaphthenic acid fractions with a high acid numher, and to more dilutelyes,-fractions with a lower acid number.

Still another object of the presentinvention are the improved alkalinesolutions of 18 B. and more containing suitable fractions of naphthenicacids.

Still another object of .the present invention is the process forimproving the wetting-out action of alkaline lyes by adding theretomixtures of Column 1 of this table gives the boiling point of thenaphthenic acid fraction.

Column 2 of this table gives the acid number of the naphthenic acidfraction.

Column 3 of this table gives the content of free alkali in the lye.

Column 4 of this table of the"lye-in B.

Column 5 of this table gives the addition of naphthenic acid in cc. perliter lye.

Column 6 of this'table gives the shrinkage of raw cotton yarn after 5seconds.

Column 7 of this table gives the shrinkage of raw cotton yarn after 10seconds.

Column 8 of this table gives the shrinkage of raw cotton yarn after 15seconds.

Column 9 of this table gives the quotient.

The following second table shows the action. in lyes of diiferentconcentration, of mixtures of a naphthenic acid fraction of the acidnumber 384 and boiling point 130-140" C. with other compounds increasingits wetting-out properties in comparison to the action of the naphthenicacid fraction "itself.

gives the concentration Column 1 of this table indicates the quantity ofnaphthenic acid added to 1 liter lye.

Column 2 of this table indicates the quantity of 55% aqueous solution ofthe sodium salt of the n-butylsulphuric acid.

Column 3 of this table indicates the concentration of the lye.

Column 4 of this table indicates the content 25 of the lye on freealkali in Column 5 of this table indicates the quotient.

Column 6 of this table indicates the shrinkage of a raw cotton yarnafter 15 seconds treatment.

Column 7 of this table indicates the nature of 30 the lye.

The following Table III shows the action of the same naphthenic acidfraction as above in mixture with the acetals obtained from glycerineand technical methylcyclohexanones.

with 1 cc. of di-(oxethyl)-n-buty1amine.

35 Table III Per- 46 Ce. Cc. Degrees cent 95:5 7.5 22.5 17.0 23.4Littlemuddy.

25:5 7.5 26 21.55 17.3 23.3 Clear.

7.6 000. 25 18.71 20.53 18.6 Clear. 30:10 7.5 25 13.71 20.53 23.6 Do.

7.5 000. 0 20 14.3 26.8 6.2 Clear. 30120 7.5 20 14.3 25.3 11.2 Do.

50 Column 1 of this table indicates the quantity of naphthenic acidadded to the lye.

. Column 2 of this table indicates the ratio of mixture of naphthenicacids with the acetals.

Column 3 of this table indicates the quantity 55 of the mixture added tothe lye.

Column 4 of this table indicates the concentration of the 'lye.

- Column 5 of this table indicates the content of the lye on free alkaliin Column 6 of this table indicates the quotient.

Column 7 of this table indicates the shrinkage of a raw cotton yarnafter seconds treatment. Column 8 of this table indicates the natureofthe lye.

Lyes possessing excellent wetting-out power may further be prepared byusing following mixtures:

1. Mix 5 cc. of naphthenic acids of acid number 356 with 7 cc. of a 49%aqueous solution of the sodium salt of the butoxyethane sulphonic acid(CI-1;CHz-CHz-CH:OCH2CH2SO3N8.) and add this mixture to a liter of lyeof 28 B.

of a raw cotton yarn after 15 seconds immersion reaches 23.8%.

2. Mix 4.5 cc. of raw naphthenic acids of acid number 291 with 10.5 cc.of isovalerianic acid and add this mixture to a liter of'lye of 30 B.Instead of isovalerianic acid, methylisobutyl acetic acid can be used,and mixed with naphthenic acid of acid number 331.

31 Mix 2.31 parts of naphthenic acids of acid number 359 with 5.39parts'of isoamyl glucoside and add this mixture to a liter of lye of 35B.

4. Add to a liter of lye of 35 B. a mixture of 5 cc. of naphthenic acidsof acid number 389 with 12 cc. of n-propylsulphate. Clear lye with goodwetting action will be obtained.

5. Add to a liter of lye of 23 B. a mixture of 9 cc. of naphthenic acidsof acid number 356 Clear lye with good wetting-out action will beobtained.

By replacing the aboveamine by monooxethylisoamylamine or bydi-(oxethyl) -isoamylamine, active wetting-out agents will be obtained.

6. Add toa liter of lye of 25 B. 5'cc. of a mixture consisting of 92parts of naphthenic acids with acid number 384 and 8 parts ofdiethyleneglycolmonobutylether or of 95 parts of naphthenic acids and 5parts of glycerine-a-isoamylether.

Clear lyes with good wetting-out action will be 3 obtained.

'7. Add to a liter of lye of 32 B. a mixture of 5 cc. of naphthenicacids of acid number 384 with 3.5 cc. of the concentrated aqueoussolution of the sodium salt of a high sulphonated ricinoleic acid. Clearand stable lyes will be obtained.

What I claim is:

1. The phenol-free alkaline lyes of 18 B. and more, possessing goodwetting out properties and containing a wetting-capacity increasingagent consisting of such fractions of naphthenic acids that the quotientacid number of the naphthenic acid fraction content in percent of thealkali in the lye is a number between 15-25.

2. The phenol-free alkaline lyes of B. and more, possessing goodwetting-out properties and containing a wetting capacity increasingagent consisting of such fractions of naphthenic acids, the acid numberof which is 380 and more and the quotient acid number of the naphthenicacid fraction content in percent of the alkali in the lye is a numberbetween 15-25.

3. The phenol-free alkaline lyes of 26-30 B., possessing goodwetting-out properties and containing a wetting capacity increasingagent consisting of such fractions of naphthenic acids, the acid numberof which is 360-380 and the quotient acid number of the naphthenic acidfraction content in percent of'the alkali in the lye is a number between15-25.

4. The phenol-free alkaline lyes of 18-26 B., possessing goodwetting-out properties and containing a wetting capacity increasingagent consisting of such fractions of naphthenic acids, the acid numberof which is 250-360 and the quotient acid of the naphthenic acidfraction content in percent of the alkali in the lye is a number between15-25.

5. A process for the alkaline treatment of cellulosic material,comprising subjecting the cellulosic material to a treatment with aphenol free alkaline lye of 18 B. and more containing a wetting capacityincreasing agent consisting of such fractions of naphthenic acids thatthe quotient acid number of the naphthenic acid fraction content inpercent of the alkali in the lye is a number between 15-25.

6. A process for the alkaline treatment of cellulosic material,comprising subjecting the cellulosic material to a treatmentwithphenolfree' alkaline lyes of 30 B. and more, containa wetting capacityincreasing agent consisting of which is 3 menace cellulosic material toa treatment with phenoliree alkaline lyes of 26-30 Ba, containing awetting capacity increasing agent consisting of fractions of gaphthenicacids, the acid number 0-380 and the quotient acid number of thenaphthenic acid fraction content in percent of the alkali in the lye isa number between 15-25. 8. A process for the alkaline treatment ofcellulosic material, comprising subjecting the c'ellulosic material-to atreatment with phenolfree alkaline lyes of 18-26 B., containing awetting capacity increasing agent consisting of fractions\ of naphthenicacids, the acid number of which is 250-360 and the quotient is a numberbetween 15-25.

